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US5376677A - Benzo[b]thiophene derivatives - Google Patents

Benzo[b]thiophene derivatives Download PDF

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US5376677A
US5376677A US08/035,485 US3548593A US5376677A US 5376677 A US5376677 A US 5376677A US 3548593 A US3548593 A US 3548593A US 5376677 A US5376677 A US 5376677A
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methyl
benzo
thienyl
methoxyacrylate
alkyl
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US08/035,485
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Stephan Trah
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Novartis Corp
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Ciba Geigy Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
    • C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/12—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings condensed with a carbocyclic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
    • C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • C07D333/60—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring

Definitions

  • the present invention relates to heterocyclic compounds, namely to benzo[b]thiophene derivatives of the general formula ##STR2## in which R is halogen, C 1-4 alkyl, C 1-4 haloalkyl, C 1-4 alkoxy-C 1-4 alkyl, aryl-C 1-4 alkoxy-C 1-4 alkyl, aryloxy-C 1-4 alkyl, heteroaryloxy-C 1-4 alkyl, arylthio-C 1-4 alkyl, heteroarylthio-C 1-4 alkyl, C 2-5 alkanoyloxy-C 1-4 alkyl (optionally C 1-4 alkyl-substituted C 3-6 cycloalkyl)-carbonyloxy-C 1-4 alkyl, aroyloxy-C 1-4 alkyl, aryl-C 2-5 alkanoyloxy-C 1-4 alkyl, heteroaryl-C 2-5 alkanoyloxy-C 1-4 alkyl, C 1-4 al
  • R 1 is aryl or heteroaryl
  • R 2 and R 3 independently of one another are hydrogen, C 1-4 alkyl, aryl-C 1-4 alkyl, aryl or heteroaryl
  • R 2 and R 3 together with the nitrogen atom to which they are bonded are a 5- or 6-membered ring which may contain an oxygen or sulfur atom,
  • R 4 and R 5 independently of one another are hydrogen, C 1-4 alkyl, C 1-4 haloalkyl, C 1-4 alkoxy-C 1-4 alkyl, C 1-4 alkylthio-C 1-4 alkyl, aryl-C 1-4 alkyl, C 3-6 cycloalkyl, aryl, heteroaryl, C 1-4 alkoxy or aroyl,
  • R 4 and, R 5 together with the carbon atom to which they are bonded are a 5- or 6-membered carbocyclic or heterocyclic ring to which one or two benzene rings may be fused,
  • R 6 is aryl, heteroaryl, C 1-4 alkoxy, aryl-C 1-4 alkoxy or C 3 or 4 alkenyloxy, and
  • R 7 and R 8 independently of one another are hydrogen, C 1-4 alkyl, aryl, heteroaryl or arylsulfonyl.
  • the compounds according to the invention have fungicidal properties and are suitable as fungicidal active substances, in particular for use in agriculture and in horticulture.
  • the invention furthermore relates to a process for the preparation of the compounds according to the invention, to fungicidal compositions which contain such compounds as active substances, and to the use of such compounds and compositions for controlling fungi in agriculture and in horticulture.
  • all "alkyl” groups as such or as part of larger groups, such as heteroarylalkyl, can be straight-chain or branched, depending on the number of their carbon atoms.
  • a halogen atom which may be present is fluorine, chlorine, bromine or iodine, fluorine, chlorine and bromine being preferred.
  • a haloalkyl group can have one or more halogen substituents which can be identical or different.
  • Aryl is understood as meaning, in particular, phenyl or naphthyl
  • heteroaryl is understood as meaning a heterocyclic group which has aromatic character, for example pyridyl, furyl, thienyl, isoxazolyl, thiazolyl, imidazolyl, pyrimidinyl or 1,3,4-thiadiazolyl, or such a group to which benzene is fused, for example, benzoxazolyl.
  • aryl or heteroaryl as part of a larger group, for example aralkyl or heteroarylalkyl.
  • Each of the aryl and heteroaryl groups can have one or more substituents, advantageously selected from amongst halogen, C 1-4 alkyl, C 1-4 haloalkyl, C 1-4 alkylthio-C 1-4 alkyl, C 1-4 alkoxy, C 1-4 haloalkoxy, aryl-C 1-4 alkoxy, C 3-6 alkenyloxy, aryloxy, C 1-4 alkylthio, C 3-6 cycloalkyl-C 1-4 alkylthio, nitro and tri(C 1-4 alkyl)silyl.
  • substituents advantageously selected from amongst halogen, C 1-4 alkyl, C 1-4 haloalkyl, C 1-4 alkylthio-C 1-4 alkyl, C 1-4 alkoxy, C 1-4 haloalkoxy, aryl-C 1-4 alkoxy, C 3-6 alkenyloxy, aryloxy, C 1-4 alkylthio, C 3-6
  • a tetrahydrofuran, dioxolane or dioxane ring can be fused to a phenyl group, so that the corresponding group is 2,3-dihydrobenzofuranyl, 1,3-benzodioxolanyl or 1,4-benzodioxanyl.
  • the 5- or 6-membered heterocyclic ring R 2 R 3 N [part of group (b)] can also be substituted, in particular by one or more C 1-4 alkyl groups.
  • the substituent R is in each case in the 4-, 5-, 6- of 7-position of the benzo[b]thiophene ring, the 5-position being preferred.
  • the compounds of the formula I contain asymmetric carbon atoms, the compounds occur in optically active form. On the basis of the presence of the aliphatic double bond alone, the compounds occur in the [E] or [Z] form in any case. Atropo-isomery can also occur.
  • the formula I is intended to embrace all these possible isomeric forms, and their mixtures, for example racemic mixtures and any [E/Z] mixtures.
  • a particular sub-group of the compounds of the formula I consists of those compounds I in which R is halogen, C 1-4 alkyl, C 1-4 haloalkyl, C 1-4 alkoxy-C 1-4 alkyl, aryloxy-C 1-4 alkyl, heteroaryloxy-C 1-4 alkyl, arylthio-C 1-4 alkyl, heteroarylthio-C 1-4 alkyl, C 1-4 alkoxy, aryloxy or one of the abovementioned groups (a) to (d), R 1 , R 2 and R 3 are as defined above, and R 4 and R 5 independently of one another are hydrogen, C 1-4 alkyl, C 1-4 haloalkyl, C 1-4 alkoxy-C 1-4 alkyl, C 3-6 cycloalkyl, aryl or heteroaryl, and R 6 is aryl or heteroaryl.
  • R' is C 1-4 alkoxy, aryl-C 1-4 alkoxy, aryloxy, heteroaryloxy, C 1-5 alkanoyloxy, (optionally C 1-4 alkyl-substituted C 3-6 cycloalkyl)carbonyloxy, aroyloxy, aryl-C 2-5 alkanoyloxy, heteroaryl-C 2-5 alkanoyloxy, arylthio, heteroarylthio, a group R 2 R 3 N (b') or a group R 4 R 5 C ⁇ NO (c'),
  • R 1 has the abovementioned meaning
  • R 6 , R 7 and R 8 are as defined above.
  • Process variant a) is the methylation of the ⁇ -hydroxy substituent of the acrylic acid derivative II.
  • This methylation step can be carried out under the reaction conditions customary for such cases.
  • the reaction is expediently carried out in an inert organic solvent such as acetone, dimethylformamide or dimethyl sulfoxide, in the presence of a base such as sodium hydride or of an alkali metal carbonate, for example sodium carbonate or potassium carbonate, at temperatures between 20° C. and 80° C., preferably in the temperature range from 40° C. to 60° C.
  • the bromination as in process variant b) can also be carried out in a manner known per se, namely expediently in an inert organic solvent such as halogenated hydrocarbon, for example carbon tetrachloride, in the presence of a radical-forming initiator, for example azoisobutyronitrile or dibenzoyl peroxide, at temperatures between 70° C. and 90° C., preferably at about 80° C.
  • a radical-forming initiator for example azoisobutyronitrile or dibenzoyl peroxide
  • the reaction as in process variant c) represents a nucleophilic substitution which is advantageously effected in an inert organic solvent such as an aliphatic or cyclic ether, for example dimethoxyethane, tetrahydrofuran or dioxane; an aliphatic ketone, for example acetone; dimethylformamide or dimethyl sulfoxide, in the presence of a base such as sodium hydride, of an alkali metal carbonate, for example sodium carbonate or potassium carbonate, or a tertiary amine, for example a trialkylamine, in particular diazabicyclononane or diazabicycloundecane, or silver oxide, at temperatures between 0° C. and 100° C., preferably in the temperature range from 20° C. to 80° C.
  • an inert organic solvent such as an aliphatic or cyclic ether, for example dimethoxyethane, tetrahydrofuran or dioxane;
  • the reaction as in process variant d) is a Wittig-Homer reaction which is expediently carried out in an inert organic solvent such as an aliphatic or cyclic ether, for example 1,2-dimethoxyethane or tetrahydrofuran, in the presence of a base, for example sodium hydride, at temperatures between 20° C. and 80° C.
  • an inert organic solvent such as an aliphatic or cyclic ether, for example 1,2-dimethoxyethane or tetrahydrofuran
  • a base for example sodium hydride
  • the condensation as in process variant e) can be carried out in a manner known per se, namely expediently in an organic solvent such as an alkanol, for example methanol or ethanol, tetrahydrofuran or pyridine, if appropriate with the addition of a catalytic amount of p-toluene sulfonic acid, at temperatures between 20° C. and 110° C.
  • an organic solvent such as an alkanol, for example methanol or ethanol, tetrahydrofuran or pyridine, if appropriate with the addition of a catalytic amount of p-toluene sulfonic acid, at temperatures between 20° C. and 110° C.
  • the compounds of the formula I which have been prepared in this manner can be isolated and purified by customary methods. Any mixtures of isomers obtained, for example E/Z isomer mixtures, can likewise be separated into the pure isomers by customers methods, for example by chromatography or fractional crystallization.
  • methyl ⁇ -(3-benzo[b]thienyl)- ⁇ -hydroxyacrylates of the formula II which are used as starting materials in process variant a) can be prepared in a manner known per se, for example as in the following equation: ##STR8##
  • dialkyl ⁇ 3-( ⁇ -methoxycarbonyl- ⁇ -methoxyvinyl)benzo[b]thienyl ⁇ methylphosphonates of the formula IV which are used as starting materials in process variant d) can be prepared in a manner known per se by reacting the corresponding methyl ⁇ -(bromomethyl-3-benzo[b]thienyl)- ⁇ -methoxyacrylate of the abovementioned formula Ib with a trialkyl ester of phosphorous acid [see, for example, Houben-Weyl, Methoden der organischen Chemie (Methods in Organic Chemistry), Vol. 12/I, 433 et seq. (1963)].
  • methyl ⁇ -(formyl-3-benzo[b]thienyl)- ⁇ -methoxyacrylates of the formula VI which are used as starting materials in process variant e) can also be prepared in a manner known per se, namely by reacting the corresponding methyl ⁇ -(bromomethyl-3-benzo[b]thienyl)- ⁇ -methoxyacrylate of the abovementioned formula Ib with sodium hydrogen carbonate and dimethyl sulfoxide [the Kornblum reaction, see, for example, J.A.C.S. 79, 6562 et seq. (1957)].
  • methyl ⁇ -(methyl-3-benzo[b]thienyl)- ⁇ -methoxyacrylates of the formula Ia which are used as starting materials in process variant b), and the methyl ⁇ -(bromomethyl-3-benzo[b]thienyl)- ⁇ -methoxyacrylates of the formula Ib which are used as starting materials in process variant c) are sub-groups of the compounds of the formula I, which can be prepared, for example, by process variant a) or b).
  • the starting materials of the formulae III, V, VII, VIII and IX are either known or can be prepared by methods known per se.
  • the compounds according to the invention have a fungicidal action and can accordingly be used for controlling fungi in agriculture, in horticulture and in wood processing. They are particularly suitable for inhibiting the growth or for destroying phytopathogenic fungi on parts of plants, for example leaves, stalks, roots, tubers, fruits or flowers and on seeds, and also harmful fungi which occur in the soil. It is furthermore possible to control wood-destroying and wood-discolouring fungi with the compounds according to the invention.
  • the compounds according to the invention are active, for example, for controlling of fungi of the classes of the Deuteromycetes, Ascomycetes, Basidiomycetes and Phycomycetes.
  • the compounds according to the invention are particularly suitable for controlling the following pathogens:
  • Powdery mildews for example Erysiphe graminis, Erysiphe cichoracearum, Podosphaera leucotricha, Uncinula necator, Sphaerotheca spp.
  • Rusts for example Puccinia tritici, Puccinia recondita, Puccinia hordei, Puccinia coronata, Puccinia striiformis, Puccinia arachidis, Hemileia vastatrix, Uromyces fabae
  • Cercospora spp. for example Cercospora arachidicola, Cercospora beticola
  • Mycosphaerella spp. for example Mycosphaerella fijiensis
  • Alternaria spp. for example Alternaria brassicae, Alternaria mali
  • Septoria spp. for example Septoria nodorum
  • Heminthosporium spp. for example Helminthosporium teres, Helminthosporium oryzae
  • Plasmopara spp. for example Plasmopara viticola
  • Pseudoperonospora spp. for example Pseudoperonospora cubensis
  • Phytophtora spp. for example Phytophtora infestans
  • Pseudocercosporella spp. for example Pseudocercosporella herpotrichoides
  • Pyricularia spp. for example Pyricularia oryzae.
  • the compounds are furthermore active for example against fungi of the genera Tilletia, Ustilago, Rhizoctonia, Verticillium, Fusarium, Pythium, Gaeumannomyces, Sclerotinia, Monilia, Botrytis, Peronospora, Bremia, Gloeosporium, Cercosporidium, Penicillium, Ceratocystis, Rhynchosporium, Pyrenophora, Diaporthe, Ramularia and Leptosphaeria.
  • Certain representatives of the compounds according to the invention also have an action against wood-destroying fungi, for example of the genera Coniophora, Gloeophyllum, Poria, Merulius, Trametes, Aureobasidium, Sclerophoma and Trichoderma.
  • the compounds according to the invention are distinguished by a prophylactic and curative action.
  • the compounds according to the invention are active against phytopathogenic fungi under greenhouse conditions at concentrations of as little as 0.5 mg up to 500 mg of active substance per liter of spray liquor.
  • dosage rates from 20 g to 1 kg of active substance of the formula I per hectare per treatment.
  • dosage rates from 0.01 g to 1.0 g of active substance of the formula I per kg of seed.
  • the compounds according to the invention can be formulated to give various compositions, for example solutions, suspensions, emulsions, emulsifiable concentrates and preparations in the form of powders.
  • the fungicidal compositions according to the invention comprise an effective amount of at least one compound of the general formula I as defined above, and formulation auxiliaries.
  • the compositions expediently contain at least one of the following formulation auxilaries:
  • Solid carriers Solid carriers; solvents or dispersants; surfactants (wetting agents and emulsifiers); dispersing agents (without surfactant action); and stabilizers.
  • Suitable solid carriers are mainly: natural minerals, such as kaolin, clays, kieselguhr, talc, bentonite, chalk, for example whiting, magnesium carbonate, limestone, quartz, dolomite, attapulgite, montmorillonite and diatomaceous earth; synthetic minerals, such as highly-disperse silica, aluminium oxide and silicates; organic substances such as cellulose, starch, urea and synthetic resins; and fertilizers, such as phosphates and nitrates, it being possible for such carriers to be, for example, in granule or powder form.
  • natural minerals such as kaolin, clays, kieselguhr, talc, bentonite, chalk, for example whiting, magnesium carbonate, limestone, quartz, dolomite, attapulgite, montmorillonite and diatomaceous earth
  • synthetic minerals such as highly-disperse silica, aluminium oxide and silicates
  • organic substances such as cellulose, starch, ure
  • Suitable solvents or dispersants are mainly: aromatics, such as toluene, xylenes, benzene and alkylnaphthalines; chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes and methylene chloride; aliphatic hydrocarbons such as cyclohexane and paraffins, for example petroleum fractions; alcohols such as butanol and glycol as well as their ethers and esters; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanones; and strongly polar solvents and dispersing agents such as dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide, such solvents or dispersing agents preferably having flashpoints of at least 30° C.
  • aromatics such as toluene, xylenes, benzene and alkylnaphthalines
  • liquified gaseous extenders or carriers are also suitable, which are products which are gaseous at room temperature and under atmospheric pressure.
  • aerosol propellants such as halohydrocarbons, for example dichlorodifluoromethane.
  • organic solvents can also be used as auxiliary solvents.
  • the surfactants can be non-ionic compounds such as condensation products of fatty acids, fatty alcohols or fat-substituted phenols with ethylene oxide; fatty acid esters and fatty acid ethers of sugars or of polyhydric alcohols; the products which are obtained from sugars or polyhydric alcohols by condensation with ethylene oxide; block polymers of ethylene oxide and propylene oxide; or alkyldimethylamine oxides.
  • the surfactants can also represent anionic compounds such as soaps; fatty sulfate esters, for example dodecyl sodium sulfate, octadecyl sodium sulfate and cetyl sodium sulfate; alkylsulfonates, arylsulfonates and fatty-aromatic sulfonates such as alkylbenzenesulfonates, for example calcium dodecylbenzenesulfonate, and butylnaphthalenesulfonates; and more complex fatty sulfonates, for example the amide condensation products of oleic acid and N-methyltaurine, and the sodium sulfonate of dioctyl succinate.
  • anionic compounds such as soaps
  • fatty sulfate esters for example dodecyl sodium sulfate, octadecyl sodium sulfate and cetyl sodium sulfate
  • the surfactants can be cationic compounds such as alkyldimethylbenzylammonium chlorides, dialkyldimethylammonium chlorides, alkyltrimethylammonium chlorides and ethoxylated quaternary ammonium chlorides.
  • lignin sodium salts and ammonium salts of lignin sulfonic acid, sodium salts of maleic anhydride/diisobutylene copolymers, sodium salts and ammonium salts of sulfonated polycondensation products of naphthalene and formaldehyde, and sulfite waste liquors.
  • dispersants which are particularly suitable as thickeners or anti-settling agents: methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, polyvinyl alcohol, alginates, caseinales and blood albumin.
  • Suitable stabilizers are acid-binding agents, for example epichlorohydrin, phenyl glycidyl ether and soya epoxides; antioxidants, for example gallic acid esters and butylhydroxytoluene; UV absorbers, for example substituted benzophenones, diphenylacrylonitrilic acid esters and cinnamic acid esters; and deactivators, for example salts of ethylenediaminetetraacetic acid, and polyglycols.
  • acid-binding agents for example epichlorohydrin, phenyl glycidyl ether and soya epoxides
  • antioxidants for example gallic acid esters and butylhydroxytoluene
  • UV absorbers for example substituted benzophenones, diphenylacrylonitrilic acid esters and cinnamic acid esters
  • deactivators for example salts of ethylenediaminetetraacetic acid, and polyglycol
  • the fungicidal compositions according to the invention can also contain other active substances, for example other fungicidal compositions, insecticidal and acaricidal compositions, bactericides, plant-growth regulators and fertilizers. Such combined preparations are suitable for widening the spectrum of action or for specifically influencing plant growth.
  • the fungicidal compositions according to the invention contain between 0.0001 and 85 percent by weight of compound according to the invention, or compounds according to the invention, as the active substance(s), depending on the nature of these compositions. They can be in a form which is suitable for storage and transport. In such forms, for example emulsifiable concentrates, the active substance concentration is usually in the upper range of the above concentration interval. These forms can then be diluted with identical or different formulation auxiliaries down to active substance concentrations which are suitable for use in practice, and such concentrations are usually in the lower range of the above concentration interval.
  • Emulsifiable concentrates generally contain 5 to 85 percent by weight, preferably 25 to 75 percent by weight, of the compound(s) according to the invention.
  • Suitable use forms are, inter alia, ready-for-use solutions, emulsions and suspensions which are suitable, for example, as spray liquors.
  • Such spray liquors can contain concentrations of between, for example, 0.0001 and 20 percent by weight.
  • the ultra-low-volume method it is possible to formulate spray liquors in which the active substance concentration is preferably from 0.5 to 20 percent by weight, while the spray liquors formulated using the low-volume method and the high-volume method preferably have an active substance concentration of 0.02 to 1.0, or 0.002 to 0.1, percent by weight.
  • the fungidical compositions according to the invention can be prepared by mixing at least one compound according to the invention with formulation auxiliaries.
  • compositions can be prepared in a known manner, for example by mixing the active substance with solid carriers, by dissolving or suspending them in suitable solvents or dispersing agents, if appropriate with the use of surfactants as wetting agents or emulsifiers or of dispersants, by diluting pre-prepared emulsifiable concentrates with solvents or dispersing agents, etc.
  • the active substance can be mixed with a solid carrier, for example by jointly grinding them; or the solid carrier can be impregnated with a solution or suspension of the active substance and the solvent or dispersing agent can then be removed by evaporation, heating or by filtering off under reduced pressure.
  • a solid carrier for example by jointly grinding them; or the solid carrier can be impregnated with a solution or suspension of the active substance and the solvent or dispersing agent can then be removed by evaporation, heating or by filtering off under reduced pressure.
  • surfactants or dispersants such compositions in the form of powders can be rendered readily wettable with water, so that they can be converted into aqueous suspensions which are suitable, for example, as spray liquors.
  • the compounds according to the invention can also be mixed with a surfactant and a solid carrier to form a wettable powder which is dispersible in water, or they can be mixed with a solid pregranulated carrier to form a granular product.
  • a compound according to the invention can be dissolved in a solvent which is not miscible with water such as, for example, an alicyclic ketone, which expediently contains dissolved emulsifier, so that the solution has a self-emulsifying effect when water is added.
  • the active substance can be mixed with an emulsifier and the mixture can then be diluted with water to the desired concentration.
  • the active substance can be dissolved in a solvent and the solution can then be mixed with an emulsifier.
  • Such a mixture can likewise be diluted with water to the desired concentration. In this manner, emulsifiable concentrates or ready-for-use emulsions are obtained.
  • compositions according to the invention can be used following the application methods customary in plant protection or in agriculture.
  • the method according to the invention for controlling fungi comprises treating the goods to be protected, for example plants, parts of plants, or seeds, with an effective amount of a compound according to the invention or of a composition according to the invention.
  • the crude product is crystallized from methylene chloride/n-hexane, and methyl ⁇ -(5-bromomethyl-3-benzo[b]thienyl)- ⁇ -methoxyacrylate is obtained in this manner as pale yellow crystals, m.p. 124°-125° C.
  • methyl ⁇ -(7-methyl-3-benzo[b]thienyl)- ⁇ -methoxyacrylate (see Example 2) is brominated with N-bromosuccinimide to give methyl ⁇ -(7-bromomethyl-3-benzo[b]thienyl- ⁇ -methoxyacrylate, m.p. 97° C.
  • An emulsifiable concentrate consists of the following:
  • a ready-for-use spray liquor of any desired concentration can be prepared by emulsifying this concentrate in water.
  • a wettable powder consists of the following:
  • the components are mixed with each other, and the mixture is ground finely in a suitable mill. Dispersion of the mixture in water gives a suspension which is suitable as a ready-for-use spray liquor.

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Abstract

The invention relates to novel compounds of the formula <IMAGE> I in which R is as defined in the description, to their preparation, to fungicidal compositions which contain such compounds as active substances, and to the use of the active substances or compositions for controlling fungi in agriculture and horticulture.

Description

This application is a continuation of now abandoned application Ser. No. 07/802,742, filed Dec. 5, 1991, now abandoned, which is a division of now abandoned application Ser. No. 07/625,765, filed Dec. 13, 1990, now abandoned.
The present invention relates to heterocyclic compounds, namely to benzo[b]thiophene derivatives of the general formula ##STR2## in which R is halogen, C1-4 alkyl, C1-4 haloalkyl, C1-4 alkoxy-C1-4 alkyl, aryl-C1-4 alkoxy-C1-4 alkyl, aryloxy-C1-4 alkyl, heteroaryloxy-C1-4 alkyl, arylthio-C1-4 alkyl, heteroarylthio-C1-4 alkyl, C2-5 alkanoyloxy-C1-4 alkyl (optionally C1-4 alkyl-substituted C3-6 cycloalkyl)-carbonyloxy-C1-4 alkyl, aroyloxy-C1-4 alkyl, aryl-C2-5 alkanoyloxy-C1-4 alkyl, heteroaryl-C2-5 alkanoyloxy-C1-4 alkyl, C1-4 alkoxy, aryloxy or one of the groups (a) to (e)
R.sup.1 CH═CH                                          (a)
R.sup.2 R.sup.3 NCH.sub.2                                  (b)
R.sup.4 R.sup.5 C═NOCH.sub.2                           (c)
R.sup.6 N═CH                                           (d)
R.sup.7 R.sup.8 N--N═CH                                (e),
R1 is aryl or heteroaryl,
R2 and R3 independently of one another are hydrogen, C1-4 alkyl, aryl-C1-4 alkyl, aryl or heteroaryl
or R2 and R3 together with the nitrogen atom to which they are bonded are a 5- or 6-membered ring which may contain an oxygen or sulfur atom,
R4 and R5 independently of one another are hydrogen, C1-4 alkyl, C1-4 haloalkyl, C1-4 alkoxy-C1-4 alkyl, C1-4 alkylthio-C1-4 alkyl, aryl-C1-4 alkyl, C3-6 cycloalkyl, aryl, heteroaryl, C1-4 alkoxy or aroyl,
or
R4 and, R5 together with the carbon atom to which they are bonded are a 5- or 6-membered carbocyclic or heterocyclic ring to which one or two benzene rings may be fused,
R6 is aryl, heteroaryl, C1-4 alkoxy, aryl-C1-4 alkoxy or C3 or 4 alkenyloxy, and
R7 and R8 independently of one another are hydrogen, C1-4 alkyl, aryl, heteroaryl or arylsulfonyl.
The compounds according to the invention have fungicidal properties and are suitable as fungicidal active substances, in particular for use in agriculture and in horticulture.
The invention furthermore relates to a process for the preparation of the compounds according to the invention, to fungicidal compositions which contain such compounds as active substances, and to the use of such compounds and compositions for controlling fungi in agriculture and in horticulture.
In the above formula I, all "alkyl" groups, as such or as part of larger groups, such as heteroarylalkyl, can be straight-chain or branched, depending on the number of their carbon atoms. A halogen atom which may be present is fluorine, chlorine, bromine or iodine, fluorine, chlorine and bromine being preferred. A haloalkyl group can have one or more halogen substituents which can be identical or different. Aryl is understood as meaning, in particular, phenyl or naphthyl, heteroaryl is understood as meaning a heterocyclic group which has aromatic character, for example pyridyl, furyl, thienyl, isoxazolyl, thiazolyl, imidazolyl, pyrimidinyl or 1,3,4-thiadiazolyl, or such a group to which benzene is fused, for example, benzoxazolyl. This is also true for aryl or heteroaryl as part of a larger group, for example aralkyl or heteroarylalkyl. Each of the aryl and heteroaryl groups can have one or more substituents, advantageously selected from amongst halogen, C1-4 alkyl, C1-4 haloalkyl, C1-4 alkylthio-C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkoxy, aryl-C1-4 alkoxy, C3-6 alkenyloxy, aryloxy, C1-4 alkylthio, C3-6 cycloalkyl-C1-4 alkylthio, nitro and tri(C1-4 alkyl)silyl. Moreover, a tetrahydrofuran, dioxolane or dioxane ring can be fused to a phenyl group, so that the corresponding group is 2,3-dihydrobenzofuranyl, 1,3-benzodioxolanyl or 1,4-benzodioxanyl. The 5- or 6-membered heterocyclic ring R2 R3 N [part of group (b)] can also be substituted, in particular by one or more C1-4 alkyl groups.
The substituent R is in each case in the 4-, 5-, 6- of 7-position of the benzo[b]thiophene ring, the 5-position being preferred.
If the compounds of the formula I contain asymmetric carbon atoms, the compounds occur in optically active form. On the basis of the presence of the aliphatic double bond alone, the compounds occur in the [E] or [Z] form in any case. Atropo-isomery can also occur. The formula I is intended to embrace all these possible isomeric forms, and their mixtures, for example racemic mixtures and any [E/Z] mixtures.
A particular sub-group of the compounds of the formula I consists of those compounds I in which R is halogen, C1-4 alkyl, C1-4 haloalkyl, C1-4 alkoxy-C1-4 alkyl, aryloxy-C1-4 alkyl, heteroaryloxy-C1-4 alkyl, arylthio-C1-4 alkyl, heteroarylthio-C1-4 alkyl, C1-4 alkoxy, aryloxy or one of the abovementioned groups (a) to (d), R1, R2 and R3 are as defined above, and R4 and R5 independently of one another are hydrogen, C1-4 alkyl, C1-4 haloalkyl, C1-4 alkoxy-C1-4 alkyl, C3-6 cycloalkyl, aryl or heteroaryl, and R6 is aryl or heteroaryl.
Particularly preferred individual compounds of the formula I are:
Methyl α{5-(α-methyl-m-trifiuoromethylbenzylideneaminooxymethyl)-3-benzo[b]thienyl}-β-methoxyacrylate,
methylα-{5-(α-[n-propyl]-benzylideneaminooxymethyl)-3-benzo[b]thienyl}-β-methoxyacrylate,
methyl α-{5-[α-(2-pyridyl)-ethylideneaminooxymethyl]-3-benzo[b]thienyl}-β-methoxyacrylate,
methyl α-{5-(α-cyclopropyl-4-chlorobenzylideneaminooxymethyl)-3-benzo[b]thienyl}-β-methoxyacrylate,
methyl α-{5-methoxy-3-benzo[b]thienyl}-β-methoxyacrylate,
methyl α-{5-ethoxy-3-benzo[b]thienyl}-β-methoxyacrylate,
methyl α-{5-[(α-phenylethyl)methylaminomethyl]-3-benzo[b]thienyl}-.beta.-methoxyacrylate,
methyl α-{5-(dicyclopropylmethylideneaminooxymethyl)-3-benzo[b]thienyl}-.beta.-methoxyacrylate,
methyl α-{5-[(cyclopropyl)(2-pyridyl)methylideneaminooxymethyl]-3-benzo[b]thienyl}-β-methoxyacrylate,
methyl α-{5-(α-cyclopropyl-m-trifluoromethylbenzylideneaminooxymethyl)-3-benzo[b]thienyl}-β-methoxyacrylate,
methyl α-{5-(α-cyclopropylbenzylideneaminooxymethyl)-3-benzo[b]thienyl}-β-methoxyacrylate,
methyl α-{5-[β-methyl-α-(2-pyridyl)-propylideneaminooxymethyl]-3-benzo[b]thienyl}-β-methoxyacrylate and
methyl α-{5-(2-isopropyl-4-methyl-2,5-dihydrothiazol-5-ylideneaminooxymethyl)-3-benzo[b]thienyl}-β-methoxyacrylate.
The process according to the invention for the preparation of the compounds of the general formula I comprises
a) to prepare those compounds of the formula I in which R is other than a group (b), (c), (d) or (e), treating a methyl α-(3-benzo[b]thienyl)-β-hydroxyacrylate of the general formula ##STR3## in which R is as defined above, with the exception of a group (b), (c), (d) or (e), with a methylating agent,
b) to prepare those compounds of the formula I in which R is bromomethyl, treating a methyl α-(methyl-3-benzo[b]thienyl)-β-methoxyacrylate of the general formula ##STR4## with N-bromosuccinimide, c) to prepare those compounds of the formula I in which R is C1-4 alkoxymethyl, aryl-C1-4 alkoxymethyl, aryloxymethyl, heteroaryloxymethyl, arylthiomethyl, heteroarylthiomethyl, C1-5 alkanoyloxymethyl, (optionally C1-4 alkyl-substituted C1-6 cycloalkyl)carbonyloxymethyl, aroyloxymethyl, aryl-C2-5 alkanoyloxymethyl, heteroaryl-C2-5 alkanoyloxymethyl, a group (b) or a group (c), reacting a methyl α-(bromomethyl-3-benzo[b]thienyl)-β-methoxyacrylate of the general formula ##STR5## with a hydroxy compound, a mercapto compound, a carboxylic acid, an amine or an oxime of the general formula
R'--H                                                      III
in which R' is C1-4 alkoxy, aryl-C1-4 alkoxy, aryloxy, heteroaryloxy, C1-5 alkanoyloxy, (optionally C1-4 alkyl-substituted C3-6 cycloalkyl)carbonyloxy, aroyloxy, aryl-C2-5 alkanoyloxy, heteroaryl-C2-5 alkanoyloxy, arylthio, heteroarylthio, a group R2 R3 N (b') or a group R4 R5 C═NO (c'),
d) to prepare those compounds of the formula I in which R is a group (a), reacting a dialkyl {3-(α-methoxycarbonyl-β-methoxyvinyl)-benzo[b]thienyl}methylphosphonate of the general formula ##STR6## in which R9 is C1-4 alkyl with an aldehyde of the general formula
R.sup.1 CHO                                                V
in which R1 has the abovementioned meaning, or
e) to prepare those compounds of the formula I in which R is a group (d) or a group (e), reacting a methyl α-(formyl-3-benzo[b]thienyl)-β-methoxyacrylate of the general formula ##STR7## with an amine, hydroxylamine or hydrazine of the general formula
R.sup.6 NH.sub.2                                           VII
or
R.sup.7 R.sup.8 N--NH.sub.2                                VIII
in which R6, R7 and R8 are as defined above.
Process variant a) is the methylation of the β-hydroxy substituent of the acrylic acid derivative II. This methylation step can be carried out under the reaction conditions customary for such cases. The reaction is expediently carried out in an inert organic solvent such as acetone, dimethylformamide or dimethyl sulfoxide, in the presence of a base such as sodium hydride or of an alkali metal carbonate, for example sodium carbonate or potassium carbonate, at temperatures between 20° C. and 80° C., preferably in the temperature range from 40° C. to 60° C.
The bromination as in process variant b) can also be carried out in a manner known per se, namely expediently in an inert organic solvent such as halogenated hydrocarbon, for example carbon tetrachloride, in the presence of a radical-forming initiator, for example azoisobutyronitrile or dibenzoyl peroxide, at temperatures between 70° C. and 90° C., preferably at about 80° C. An example of such a bromination is described by Homer et at. in Angew. Chem. 71, 349-365 (1959).
The reaction as in process variant c) represents a nucleophilic substitution which is advantageously effected in an inert organic solvent such as an aliphatic or cyclic ether, for example dimethoxyethane, tetrahydrofuran or dioxane; an aliphatic ketone, for example acetone; dimethylformamide or dimethyl sulfoxide, in the presence of a base such as sodium hydride, of an alkali metal carbonate, for example sodium carbonate or potassium carbonate, or a tertiary amine, for example a trialkylamine, in particular diazabicyclononane or diazabicycloundecane, or silver oxide, at temperatures between 0° C. and 100° C., preferably in the temperature range from 20° C. to 80° C.
The reaction as in process variant d) is a Wittig-Homer reaction which is expediently carried out in an inert organic solvent such as an aliphatic or cyclic ether, for example 1,2-dimethoxyethane or tetrahydrofuran, in the presence of a base, for example sodium hydride, at temperatures between 20° C. and 80° C. Examples of such a reaction can be found in J.A.C.S. 83, 1733-1738 (1961) (Wadsworth et al.).
The condensation as in process variant e) can be carried out in a manner known per se, namely expediently in an organic solvent such as an alkanol, for example methanol or ethanol, tetrahydrofuran or pyridine, if appropriate with the addition of a catalytic amount of p-toluene sulfonic acid, at temperatures between 20° C. and 110° C.
The compounds of the formula I which have been prepared in this manner can be isolated and purified by customary methods. Any mixtures of isomers obtained, for example E/Z isomer mixtures, can likewise be separated into the pure isomers by customers methods, for example by chromatography or fractional crystallization.
The methyl α-(3-benzo[b]thienyl)-β-hydroxyacrylates of the formula II which are used as starting materials in process variant a) can be prepared in a manner known per se, for example as in the following equation: ##STR8##
The dialkyl {3-(α-methoxycarbonyl-β-methoxyvinyl)benzo[b]thienyl}methylphosphonates of the formula IV which are used as starting materials in process variant d) can be prepared in a manner known per se by reacting the corresponding methyl α-(bromomethyl-3-benzo[b]thienyl)-β-methoxyacrylate of the abovementioned formula Ib with a trialkyl ester of phosphorous acid [see, for example, Houben-Weyl, Methoden der organischen Chemie (Methods in Organic Chemistry), Vol. 12/I, 433 et seq. (1963)].
The methyl α-(formyl-3-benzo[b]thienyl)-β-methoxyacrylates of the formula VI which are used as starting materials in process variant e) can also be prepared in a manner known per se, namely by reacting the corresponding methyl α-(bromomethyl-3-benzo[b]thienyl)-β-methoxyacrylate of the abovementioned formula Ib with sodium hydrogen carbonate and dimethyl sulfoxide [the Kornblum reaction, see, for example, J.A.C.S. 79, 6562 et seq. (1957)].
The methyl α-(methyl-3-benzo[b]thienyl)-β-methoxyacrylates of the formula Ia which are used as starting materials in process variant b), and the methyl α-(bromomethyl-3-benzo[b]thienyl)-β-methoxyacrylates of the formula Ib which are used as starting materials in process variant c) are sub-groups of the compounds of the formula I, which can be prepared, for example, by process variant a) or b). The starting materials of the formulae III, V, VII, VIII and IX are either known or can be prepared by methods known per se.
The compounds according to the invention have a fungicidal action and can accordingly be used for controlling fungi in agriculture, in horticulture and in wood processing. They are particularly suitable for inhibiting the growth or for destroying phytopathogenic fungi on parts of plants, for example leaves, stalks, roots, tubers, fruits or flowers and on seeds, and also harmful fungi which occur in the soil. It is furthermore possible to control wood-destroying and wood-discolouring fungi with the compounds according to the invention. The compounds according to the invention are active, for example, for controlling of fungi of the classes of the Deuteromycetes, Ascomycetes, Basidiomycetes and Phycomycetes.
The compounds according to the invention are particularly suitable for controlling the following pathogens:
Powdery mildews (for example Erysiphe graminis, Erysiphe cichoracearum, Podosphaera leucotricha, Uncinula necator, Sphaerotheca spp.)
Rusts (for example Puccinia tritici, Puccinia recondita, Puccinia hordei, Puccinia coronata, Puccinia striiformis, Puccinia arachidis, Hemileia vastatrix, Uromyces fabae)
Scabs (for example Venturia inaequalis)
Cercospora spp. (for example Cercospora arachidicola, Cercospora beticola)
Mycosphaerella spp. (for example Mycosphaerella fijiensis)
Alternaria spp. (for example Alternaria brassicae, Alternaria mali)
Septoria spp. (for example Septoria nodorum)
Heminthosporium spp. (for example Helminthosporium teres, Helminthosporium oryzae)
Plasmopara spp. (for example Plasmopara viticola)
Pseudoperonospora spp. (for example Pseudoperonospora cubensis)
Phytophtora spp. (for example Phytophtora infestans)
Pseudocercosporella spp. (for example Pseudocercosporella herpotrichoides)
Pyricularia spp. (for example Pyricularia oryzae).
The compounds are furthermore active for example against fungi of the genera Tilletia, Ustilago, Rhizoctonia, Verticillium, Fusarium, Pythium, Gaeumannomyces, Sclerotinia, Monilia, Botrytis, Peronospora, Bremia, Gloeosporium, Cercosporidium, Penicillium, Ceratocystis, Rhynchosporium, Pyrenophora, Diaporthe, Ramularia and Leptosphaeria. Certain representatives of the compounds according to the invention also have an action against wood-destroying fungi, for example of the genera Coniophora, Gloeophyllum, Poria, Merulius, Trametes, Aureobasidium, Sclerophoma and Trichoderma.
The compounds according to the invention are distinguished by a prophylactic and curative action.
The compounds according to the invention are active against phytopathogenic fungi under greenhouse conditions at concentrations of as little as 0.5 mg up to 500 mg of active substance per liter of spray liquor. In the open, it is advantageous to use dosage rates from 20 g to 1 kg of active substance of the formula I per hectare per treatment. To control seed- or soil-borne fungi by seed dressing, it is advantageous to use dosage rates from 0.01 g to 1.0 g of active substance of the formula I per kg of seed.
The compounds according to the invention can be formulated to give various compositions, for example solutions, suspensions, emulsions, emulsifiable concentrates and preparations in the form of powders. The fungicidal compositions according to the invention comprise an effective amount of at least one compound of the general formula I as defined above, and formulation auxiliaries. The compositions expediently contain at least one of the following formulation auxilaries:
Solid carriers; solvents or dispersants; surfactants (wetting agents and emulsifiers); dispersing agents (without surfactant action); and stabilizers.
Suitable solid carriers are mainly: natural minerals, such as kaolin, clays, kieselguhr, talc, bentonite, chalk, for example whiting, magnesium carbonate, limestone, quartz, dolomite, attapulgite, montmorillonite and diatomaceous earth; synthetic minerals, such as highly-disperse silica, aluminium oxide and silicates; organic substances such as cellulose, starch, urea and synthetic resins; and fertilizers, such as phosphates and nitrates, it being possible for such carriers to be, for example, in granule or powder form.
Suitable solvents or dispersants are mainly: aromatics, such as toluene, xylenes, benzene and alkylnaphthalines; chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes and methylene chloride; aliphatic hydrocarbons such as cyclohexane and paraffins, for example petroleum fractions; alcohols such as butanol and glycol as well as their ethers and esters; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanones; and strongly polar solvents and dispersing agents such as dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide, such solvents or dispersing agents preferably having flashpoints of at least 30° C. and boiling points of at least 50° C., and water. From amongst the solvents and dispersing agents, so-called liquified gaseous extenders or carriers are also suitable, which are products which are gaseous at room temperature and under atmospheric pressure. Examples of such products, are in particular, aerosol propellants such as halohydrocarbons, for example dichlorodifluoromethane. In the event that water is used as the solvent, for example organic solvents can also be used as auxiliary solvents.
The surfactants (wetting agents and emulsifiers) can be non-ionic compounds such as condensation products of fatty acids, fatty alcohols or fat-substituted phenols with ethylene oxide; fatty acid esters and fatty acid ethers of sugars or of polyhydric alcohols; the products which are obtained from sugars or polyhydric alcohols by condensation with ethylene oxide; block polymers of ethylene oxide and propylene oxide; or alkyldimethylamine oxides.
The surfactants can also represent anionic compounds such as soaps; fatty sulfate esters, for example dodecyl sodium sulfate, octadecyl sodium sulfate and cetyl sodium sulfate; alkylsulfonates, arylsulfonates and fatty-aromatic sulfonates such as alkylbenzenesulfonates, for example calcium dodecylbenzenesulfonate, and butylnaphthalenesulfonates; and more complex fatty sulfonates, for example the amide condensation products of oleic acid and N-methyltaurine, and the sodium sulfonate of dioctyl succinate.
Finally, the surfactants can be cationic compounds such as alkyldimethylbenzylammonium chlorides, dialkyldimethylammonium chlorides, alkyltrimethylammonium chlorides and ethoxylated quaternary ammonium chlorides.
The following are mainly suitable as dispersants (without surfactant action): lignin, sodium salts and ammonium salts of lignin sulfonic acid, sodium salts of maleic anhydride/diisobutylene copolymers, sodium salts and ammonium salts of sulfonated polycondensation products of naphthalene and formaldehyde, and sulfite waste liquors.
The following are examples which can be employed as dispersants which are particularly suitable as thickeners or anti-settling agents: methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, polyvinyl alcohol, alginates, caseinales and blood albumin.
Examples of suitable stabilizers are acid-binding agents, for example epichlorohydrin, phenyl glycidyl ether and soya epoxides; antioxidants, for example gallic acid esters and butylhydroxytoluene; UV absorbers, for example substituted benzophenones, diphenylacrylonitrilic acid esters and cinnamic acid esters; and deactivators, for example salts of ethylenediaminetetraacetic acid, and polyglycols.
Besides the active substances of the formula I, the fungicidal compositions according to the invention can also contain other active substances, for example other fungicidal compositions, insecticidal and acaricidal compositions, bactericides, plant-growth regulators and fertilizers. Such combined preparations are suitable for widening the spectrum of action or for specifically influencing plant growth.
In general, the fungicidal compositions according to the invention contain between 0.0001 and 85 percent by weight of compound according to the invention, or compounds according to the invention, as the active substance(s), depending on the nature of these compositions. They can be in a form which is suitable for storage and transport. In such forms, for example emulsifiable concentrates, the active substance concentration is usually in the upper range of the above concentration interval. These forms can then be diluted with identical or different formulation auxiliaries down to active substance concentrations which are suitable for use in practice, and such concentrations are usually in the lower range of the above concentration interval. Emulsifiable concentrates generally contain 5 to 85 percent by weight, preferably 25 to 75 percent by weight, of the compound(s) according to the invention. Suitable use forms are, inter alia, ready-for-use solutions, emulsions and suspensions which are suitable, for example, as spray liquors. Such spray liquors can contain concentrations of between, for example, 0.0001 and 20 percent by weight. Using the ultra-low-volume method, it is possible to formulate spray liquors in which the active substance concentration is preferably from 0.5 to 20 percent by weight, while the spray liquors formulated using the low-volume method and the high-volume method preferably have an active substance concentration of 0.02 to 1.0, or 0.002 to 0.1, percent by weight.
The fungidical compositions according to the invention can be prepared by mixing at least one compound according to the invention with formulation auxiliaries.
The compositions can be prepared in a known manner, for example by mixing the active substance with solid carriers, by dissolving or suspending them in suitable solvents or dispersing agents, if appropriate with the use of surfactants as wetting agents or emulsifiers or of dispersants, by diluting pre-prepared emulsifiable concentrates with solvents or dispersing agents, etc.
In the case of compositions in the form of powders, the active substance can be mixed with a solid carrier, for example by jointly grinding them; or the solid carrier can be impregnated with a solution or suspension of the active substance and the solvent or dispersing agent can then be removed by evaporation, heating or by filtering off under reduced pressure. By adding surfactants or dispersants, such compositions in the form of powders can be rendered readily wettable with water, so that they can be converted into aqueous suspensions which are suitable, for example, as spray liquors.
The compounds according to the invention can also be mixed with a surfactant and a solid carrier to form a wettable powder which is dispersible in water, or they can be mixed with a solid pregranulated carrier to form a granular product.
If desired, a compound according to the invention can be dissolved in a solvent which is not miscible with water such as, for example, an alicyclic ketone, which expediently contains dissolved emulsifier, so that the solution has a self-emulsifying effect when water is added. On the other hand, the active substance can be mixed with an emulsifier and the mixture can then be diluted with water to the desired concentration. Moreover, the active substance can be dissolved in a solvent and the solution can then be mixed with an emulsifier. Such a mixture can likewise be diluted with water to the desired concentration. In this manner, emulsifiable concentrates or ready-for-use emulsions are obtained.
The compositions according to the invention can be used following the application methods customary in plant protection or in agriculture. The method according to the invention for controlling fungi comprises treating the goods to be protected, for example plants, parts of plants, or seeds, with an effective amount of a compound according to the invention or of a composition according to the invention.
The examples below illustrate the invention.
I. Preparation of the active substances of the formula I:
EXAMPLE 1
A solution of 79.7 g of methyl 5-methyl-3-benzo[b]thienylacetate in 200 ml of dimethylformamide and 200 ml of methyl formate is slowly added dropwise to a suspension of 10.4 g of sodium hydride in 100 ml of dimethylformamide. The reaction mixture is stirred for 2 hours at room temperature and then acidified with dilute hydrochloric acid, and this is then extracted with ethyl acetate. The organic phase is washed with water, dried over anhydrous sodium sulfate and concentrated under reduced pressure. In this manner, methyl α-(5-methyl-3-benzo[b]thienyl)-β-hydroxyacrylate is obtained as the crude product which is used unpurified as the starting material in the next process step.
The above starting material together with 36 ml of dimethyl sulfate, 69 g of potassium carbonate and 315 ml of acetone is refluxed for 2 hours. The mixture is cooled to room temperature and filtered, and the filtrate is concentrated under reduced pressure and thus gives a yellow oil. This oil is purified by chromatography on silica gel using diethyl ether/n-hexane (1:1). The crude product is recrystallized from methylene chloride/n-hexane, which gives methyl α-(5-methyl-3-benzo[b]thienyl)-β-methoxyacrylate as yellow crystals, m.p. 11420 -115° C.
EXAMPLES 2-10
Analogously to the process described in Example 1, the substituted methyl 3-benzo[b]thienylacetate in question is reacted with methyl formate to give the corresponding methyl α-(3-benzo[b]thienyl)-β-hydroxyacrylate, and the latter is subsequently methylated using dimethyl sulfate to prepare the compounds of the formula I listed in Table 1 below:
              TABLE 1                                                     
______________________________________                                    
 ##STR9##                                                                 
Example      R           Physical data                                    
______________________________________                                    
2            7-methyl    m.p. 89-90° C.                            
3            5-tert-butyl                                                 
                         [E] isomer: oil                                  
                         [Z] isomer: oil                                  
4            5-methoxy   m.p. 112-113° C.                          
5            7-methoxy   m.p. 115-116° C.                          
6            6-methoxy   m.p. 127-128° C.                          
7            5-bromo     m.p. 136-137° C.                          
8            5-chloro    m.p. 119° C.                              
9            5-ethoxy    m.p. 130° C.                              
10           5-phenoxy   oil                                              
______________________________________
EXAMPLE 11
A mixture of 71 g of methyl α-(5-methyl-3-benzo[b]thienyl)-β-methoxyacrylate (see Example 1 ), 57.8 g of N-bromosuccinimide, 1.1 g of azodiisobutyronitrile and 720 ml of carbon tetrachloride is refluxed for 75 minutes. The mixture is cooled to room temperature and filtered, and the filtrate is then concentrated under reduced pressure, and the yellow oil which remains is purified by chromatography on silica gel using diethyl ether/n-hexane (1:1). The crude product is crystallized from methylene chloride/n-hexane, and methyl α-(5-bromomethyl-3-benzo[b]thienyl)-β-methoxyacrylate is obtained in this manner as pale yellow crystals, m.p. 124°-125° C.
EXAMPLE 12
Analogously to the process described in Example 11, methyl α-(7-methyl-3-benzo[b]thienyl)-β-methoxyacrylate (see Example 2) is brominated with N-bromosuccinimide to give methyl α-(7-bromomethyl-3-benzo[b]thienyl-β-methoxyacrylate, m.p. 97° C.
EXAMPLE 13
A mixture of 1 g of methyl α-(5-bromomethyl-3-benzo[b]-thienyl)-β-methoxyacrylate (see Example 11 ), 0.28 g of phenol and 2 g of potassium carbonate in 20 ml of dimethylformamide is heated for 2 hours at 50° C. The mixture is cooled to room temperature and filtered, and the filtrate is then concentrated under reduced pressure, and the crude product is purified by chromatography on silica gel using diethyl ether/n-hexane (1:1). Recrystallization from methylene chloride/n-hexane gives methyl α-(5-phenoxymethyl-3-benzo[b]thienyl)-β-methoxyacrylate as colourless crystals, m.p. 130° C.
EXAMPLES 14-55
Analogously to the process described in Example 13, methyl α-(5-bromomethyl-3-benzo[b]thienyl)-β-methoxyacrylate is reacted with the hydroxy or mercapto compound, the carboxylic acid or the amine in question, of the formula HI, to prepare the compounds of the formula I listed in Table 2 below:
              TABLE 2                                                     
______________________________________                                    
 ##STR10##                                                                
Example                                                                   
       R                   Physical data                                  
______________________________________                                    
14     5-[(5-methyl-3-isoxazolyl)-                                        
                           m.p. 127° C.                            
       oxymethyl]                                                         
15     5-(3-nitrophenoxymethyl)                                           
                           m.p. 128° C.                            
16     5-(3-fluorophenoxymethyl)                                          
                           m.p. 109-110° C.                        
17     5-(α,α,α-trifluoro-m-                            
                           m.p. 83° C.                             
       tolyloxymethyl)                                                    
18     5-(3-chlorophenoxymethyl)                                          
                           m.p. 111-112° C.                        
19     5-(4-chlorophenoxymethyl)                                          
                           m.p. 141° C.                            
20     5-(m-tolyloxymethyl)                                               
                           m.p. 131-132° C.                        
21     5-(p-tolyloxymethyl)                                               
                           m.p. 142-143° C.                        
22     5-(3-ethylphenoxymethyl)                                           
                           m.p. 82° C.                             
23     5-(4-ethylphenoxymethyl)                                           
                           m.p. 109-110° C.                        
24     5-(4-tert-butyl-phenoxy-                                           
                           m.p. 124-125° C.                        
       methyl)                                                            
25     5-(4-nitro-m-tolyloxymethyl)                                       
                           m.p. 140-141° C.                        
26     5-(4-chloro-m-tolyloxymethyl)                                      
                           m.p. 118-119° C.                        
27     5-phenylthiomethyl  m.p. 95-96° C.                          
28     5-[5-(cyclopropylmethyl-                                           
                           oil                                            
       thio)-1,3,4-thiadiazol-2-yl-                                       
       thiomethyl]                                                        
29     5-(4-chlorophenylthiomethyl)                                       
                           m.p. 133° C.                            
30     5-(p-tolylthiomethyl)                                              
                           m.p. 125° C.                            
31     5-(4-tert-butyl-phenylthio-                                        
                           m.p. 131-132° C.                        
       methyl)                                                            
32     5-(2-benzoxazolylthiomethyl)                                       
                           m.p. 117-118° C.                        
33     5-piperidinomethyl  m.p. 105-106° C.                        
34     5-(2,6-dimethylmorpholino-                                         
                           oil                                            
       methyl)                                                            
35     5-[(α-phenylethyl)methyl-                                    
                           oil                                            
       aminomethyl]                                                       
36     5-[(5-methyl-3-isoxazolyl)-                                        
                           oil                                            
       methylaminomethyl]                                                 
37     5-[(1-naphthylmethyl)methyl-                                       
                           oil                                            
       aminomethyl]                                                       
38     5-(3,4-dimethylphenoxy-                                            
                           m.p. 134-135° C.                        
       methyl)                                                            
39     5-anilinomethyl     m.p. 141-142° C.                        
40     5-(α,α,α-trifluoro-                              
                           oil                                            
       m-tolylaminomethyl)                                                
41     5-(3-bromophenoxymethyl)                                           
                           m.p. 114-115° C.                        
42     5-[(m-tolyl)methylamino-                                           
                           oil                                            
       methyl]                                                            
43     5-(8-quinolinyloxymethyl)                                          
                           oil                                            
44     5-methoxymethyl     oil                                            
45     5-(α-methylbenzyloxy-                                        
                           oil                                            
       methyl)                                                            
46     5-[(1-methylcyclopropyl)                                           
                           oil                                            
       carbonyloxymethyl                                                  
47     5-(benzylmethylaminomethyl)                                        
                           oil                                            
48     5-(4,6-dimethylpyrimidin-                                          
                           m.p. 118-120° C.                        
       2-ylthiomethyl)                                                    
49     5-(3-pyridylacetoxymethyl)                                         
                           m.p. 77-78° C.                          
50     5-(α,α,α-trifluoro-p-                            
                           m.p. 105-106° C.                        
       tolylacetoxymethyl)                                                
51     5-(2,4-dichlorobenzoyloxy                                          
                           m.p. 119° C.                            
       methyl)                                                            
52     5-cyclopropylcarbonyloxy-                                          
                           oil                                            
       methyl                                                             
53     5-(2,4-dichlorophenyl-                                             
                           m.p. 99-100° C.                         
       acetoxymethyl)                                                     
54     5-(3-benzo[b]thienyl-                                              
                           oil                                            
       acetoxymethyl                                                      
55     5-(3,4-dichlorophenyl-                                             
                           oil                                            
       acetoxymethyl)                                                     
______________________________________
EXAMPLE 56
To 77 mg of sodium hydride in 20 ml of dimethylformamide there are added 1 g of methyl α-(5-bromomethyl-3-benzo[b]thienyl)-β-methoxyacrylate (see Example 11 ) and 0.59 g of 3-trifluoromethylacetophenone oxime. After the reaction mixture has been stirred for 15 minutes, saturated sodium hydrogen carbonate solution is added and the mixture is extracted three times using ethyl acetate. The organic phase is dried over anhydrous sodium sulfate and then concentrated. The yellow oil which remains is purified by chromatography on silica gel using diethyl ether/n-hexane (1:1) and recrystallized from diethyl ether/n-hexane. This gives methyl α-[5-(α-methyl-m-trifluoromethylbenzylideneaminooxymethyl)-3-benzo[b]thienyl]-β-methoxyacrylate as colourless crystals, m.p. 110°-111 ° C.
EXAMPLES 57-184
Analogously to the process described in Example 56, methyl α-(5-bromomethyl-3-benzo[b]thienyl)-β-methoxyacrylate is reacted with the oxime in question, of the formula III, to give the compounds of the formula I listed in Table 3 below:
                                  TABLE 3                                 
__________________________________________________________________________
 ##STR11##                                                                
     Position of                 Physical                                 
Example                                                                   
     R.sup.4 R.sup.5 CNOCH.sub.2 data                                     
__________________________________________________________________________
               R.sup.4   R.sup.5                                          
 57  5-        phenyl    trifluoromethyl                                  
                                 oil                                      
 58  5-        phenyl    methyl  m.p. 123° C.                      
 59  5-        4-chlorophenyl                                             
                         methyl  m.p. 135-136° C.                  
 60  5-        2-thienyl methyl  m.p. 111-112° C.                  
 61  5-        m-tolyl   hydrogen                                         
                                 m.p. 86-87° C.                    
 62  5-        3-chlorophenyl                                             
                         methyl  m.p. 121-122° C.                  
 63  5-        3,4-dichlorophenyl                                         
                         methyl  m.p. 149-150° C.                  
 64  5-        4-nitrophenyl                                              
                         methyl  m.p. 161° C.                      
 65  5-        phenyl    n-propyl                                         
                                 oil                                      
 66  5-        cyclopropyl                                                
                         cyclopropyl                                      
                                 oil                                      
 67  5-        2-furyl   methyl  m.p. 109° C.                      
 68  5-        2-pyridyl methyl  m.p. 107-109° C.                  
 69  5-        3-pyridyl methyl  m.p. 124-125° C.                  
 70  5-        4-chlorophenyl                                             
                         n-propyl                                         
                                 oil                                      
 71  5-        4-chlorophenyl                                             
                         cyclopropyl                                      
                                 oil                                      
 72  5-        3-fluoro-5-tri-                                            
                         methyl  m.p. 92-93° C.                    
               fluoromethyl-phenyl                                        
 73  5-        3,5-difluorophenyl                                         
                         methyl  m.p. 129-130° C.                  
 74  5-        3-fluorophenyl                                             
                         methyl  m.p. 129-130° C.                  
 75  5-        3-trifluoromethoxy-                                        
                         methyl  m.p. 75-76° C.                    
               phenyl                                                     
 76  5-        2,5-dimethyl-3-                                            
                         methyl  m.p. 78° C.                       
               furyl                                                      
 77  5-        3-thienyl methyl  m.p. 130-131° C.                  
 78  5-        2-thienyl cyclopropyl                                      
                                 oil                                      
 79  5-        3-methoxyphenyl                                            
                         methyl  m.p. 99° C.                       
 80  5-        4-tert-butyl-phenyl                                        
                         methyl  m.p. 95° C.                       
 81  5-        4-difluoromethoxy-                                         
                         methyl  m.p. 98° C.                       
               phenyl                                                     
 82  5-        α,α,α-tri-                               
                         trifluoromethyl                                  
                                 oil                                      
               fluoro-m-tolyl                                             
 83  5-        α,α,α-tri-                               
                         ethyl   oil                                      
               fluoro-m-tolyl                                             
 84  5-        3-chlorophenyl                                             
                         ethyl   m.p. 81-82° C.                    
 85  5-        α,α,α-tri-                               
                         n-propyl                                         
                                 oil                                      
               fluoro-m-tolyl                                             
 86  5-        α,α,α-tri-                               
                         methoxymethyl                                    
                                 m.p. 101-102° C.                  
               fluoro-m-tolyl                                             
 87  5-        methyl    methyl  m.p. 102-103° C.                  
 88  5-        isopropyl methyl  m.p. 69-70°  C.                   
 89  5-        1-methyl-2-                                                
                         methyl  m.p. 149° C.                      
               pyrrolyl                                                   
 90  5-        2-pyridyl cyclopropyl                                      
                                 oil                                      
 91  5-        2-thiazolyl                                                
                         cyclopropyl                                      
                                 1. isomers:                              
                                 m.p. 146-147° C.                  
                                 2. isomers:                              
                                 m.p. 92-93° C.                    
 92  5-        3-bromophenyl                                              
                         methyl  m.p. 112° C.                      
 93  5-        α,α,α-tri-                               
                         cyclopropyl                                      
                                 oil                                      
               fluoro-m-tolyl                                             
 94  5-        4-fluorophenyl                                             
                         cyclopropyl                                      
                                 m.p. 97-99° C.                    
 95  5-        4-pyridyl methyl  m.p. 159-160° C.                  
 96  5-        phenyl    cyclopropyl                                      
                                 oil                                      
 97  5-        3-chlorophenyl                                             
                         cyclopropyl                                      
                                 oil                                      
 98  5-        3-trimethylsilyl-                                          
                         cyclopropyl                                      
                                 oil                                      
               phenyl                                                     
 99  5-        2-pyridyl isopropyl                                        
                                 oil                                      
100  5-        2-pyridyl trifluoromethyl                                  
                                 m.p. 110° C.                      
101  5-        4-fluoro-3-tri-                                            
                         cyclopropyl                                      
                                 oil                                      
               fluoromethyl-phenyl                                        
102  5-        3-fluoro-5-trifluoro-                                      
                         cyclopropyl                                      
                                 oil                                      
               methyl-phenyl                                              
103  5-        3-fluorophenyl                                             
                         cyclopropyl                                      
                                 oil                                      
104  5-        cyclopropyl                                                
                         methyl  [E] isomers:                             
                                 m.p. 112-114° C.                  
                                 [Z] isomers:                             
                                 oil                                      
105  5-        3-bromophenyl                                              
                         cyclopropyl                                      
                                 oil                                      
106  5-        n-propyl  methyl  oil                                      
107  5-        ethyl     methyl  oil                                      
108  5-        isobutyl  methyl  oil                                      
109  5-        cyclohexyl                                                 
                         methyl  oil                                      
110  5-        benzyl    methyl  oil                                      
111  5-        α,α,α-                                   
                         hydrogen                                         
                                 m.p. 117° C.                      
               trifluoro-m-tolyl                                          
112  5-        α,α,α-                                   
                         isopropyl                                        
                                 oil                                      
               trifluoro-m-tolyl                                          
113  5-        2-methylthio-5-                                            
                         methyl  oil                                      
               trifluoromethyl-                                           
               phenyl                                                     
114  5-        4-fluorophenyl                                             
                         methyl  m.p. 138-140° C.                  
115  5-        3-fluorophenyl                                             
                         n-propyl                                         
                                 oil                                      
116  5-        3,4-dichlorophenyl                                         
                         hydrogen                                         
                                 m.p. 157-159° C.                  
117  5-        2-pyridyl hydrogen                                         
                                 m.p. 82° C.                       
118  5-        3-fluorophenyl                                             
                         hydrogen                                         
                                 m.p. 112-114° C.                  
119  5-        p-tolyl   methyl  m.p. 116-117° C.                  
120  5-        4-methoxy-3-methyl-                                        
                         methyl  m.p. 123-124° C.                  
               thiomethyl-phenyl                                          
121  5-        3-ethylphenyl                                              
                         methyl  oil                                      
122  5-        α,α,α-                                   
                         hydrogen                                         
                                 m.p. 165-166° C.                  
               trifluoro-p-tolyl                                          
123  5-        3-bromophenyl                                              
                         methoxyphenyl                                    
                                 m.p. 116-117° C.                  
124  5-        4-iodophenyl                                               
                         methyl  m.p. 144-145° C.                  
125  5-        ethoxy    methyl  oil                                      
126  5-        phenyl    phenyl  m.p. 141-142° C.                  
127  5-        benzoyl   methyl  m.p. 95-96° C.                    
128  5-        2-thiazolyl                                                
                         hydrogen                                         
                                 m.p. 215-217° C.                  
129  5-        3-(3-methyl-2-                                             
                         methyl  oil                                      
               butenyloxy)-phenyl                                         
130  5-        3-trimethylsilyl-                                          
                         trifluoromethyl                                  
                                 oil                                      
               phenyl                                                     
131  5-        2-thienyl tert-butyl                                       
                                 m.p. 131° C.                      
132  5-        3-(α,α,α-                                
                         hydrogen                                         
                                 oil                                      
               trifluoro-m-tolyl-                                         
               oxy)-phenyl                                                
133  5-        2-thiazolyl                                                
                         n-propyl                                         
                                 m.p. 111-112° C.                  
134  5-        2-thienyl n-propyl                                         
                                 oil                                      
135  5-        5-(2,3-dihydro-                                            
                         methyl  oil                                      
               benzofuranyl)                                              
136  5-        6-(1,4-benzo-                                              
                         methyl  oil                                      
               dioxanyl)                                                  
137  5-        2-thienyl ethyl   m.p. 86-87° C.                    
138  5-        2,5-dimethyl-3-                                            
                         methyl  m.p. 110-111° C.                  
               thienyl                                                    
139  5-        3-benzyloxyphenyl                                          
                         methyl  oil                                      
140  5-        2-thienyl hydrogen                                         
                                 oil                                      
141  5-        3-thienyl hydrogen                                         
                                 oil                                      
142  5-        phenyl    methylthiomethyl                                 
                                 oil                                      
143  5-        phenyl    methoxymethyl                                    
                                 oil                                      
144  5-        2,5-difluorophenyl                                         
                         methyl  m.p. 123-124° C.                  
145  5-        3-chloro-4-fluoro-                                         
                         methyl  m.p. 148-150° C.                  
               phenyl                                                     
146  5-        p-(n-propyl)-                                              
                         methyl  m.p. 99-100° C.                   
               phenyl                                                     
147  5-        4-fluoro-3-trifluoro-                                      
                         isopropyl                                        
                                 oil                                      
               methyl-phenyl                                              
148  5-        4-fluoro-3-trifluoro-                                      
                         methoxymethyl                                    
                                 oil                                      
               methyl-phenyl                                              
149  5-        3-bromophenyl                                              
                         isopropyl                                        
                                 oil                                      
150  5-        3-chlorophenyl                                             
                         isopropyl                                        
                                 oil                                      
151  5-        3-bromophenyl                                              
                         n-propyl                                         
                                 oil                                      
152  5-        3-chlorophenyl                                             
                         n-propyl                                         
                                 oil                                      
153  5-        4-fluoro-3-trifluoro-                                      
                         n-propyl                                         
                                 oil                                      
               methyl-phenyl                                              
__________________________________________________________________________
                ##STR12##                                                 
__________________________________________________________________________
154  5-        3-methyl-5,6-dihydro-2H-1,4-                               
                                 m.p. 158- 159° C.                 
               thiazin-2-ylidene                                          
155  5-        3-ethyl-5,6-dihydro-2H-1,4-                                
                                 m.p. 106° C.                      
               thiazin-2-ylidene                                          
156  5-        3-isopropyl-5,6-dihydro-2H-1,4-                            
                                 m.p. 119-120° C.                  
               thiazin-2-ylidene                                          
157  5-        3-cyclopropyl-5,6-dihydro-2H-1,4-                          
                                 m.p. 159-160° C.                  
               thiazin-2-ylidene                                          
158  5-        3-phenyl-5,6-dihydro-2H-1,4-                               
                                 m.p. 129-130° C.                  
               thiazin-2-ylidene                                          
159  5-        2,4-dimethyl-2,4-dihydro-thiazol-5-                        
                                 m.p. 137-138° C.                  
               ylidene           oil                                      
160  5-        2-isopropyl-4-methyl-2,5-dihydro-                          
               thiazol-5-ylidene oil                                      
161  5-        3-(4-chlorophenyl)-5,6-dihydro-2H-                         
               1,4-thiazin-2-ylidene                                      
                                 m.p. 111-112° C.                  
162  5-        2-ethyl-2,4-dimethyl-2,5-dihydro-                          
               thiazol-5-ylidene m.p. 113-114° C.                  
163  5-        2,2-dimethyl-4-isopropyl-2,5-                              
               dihydro-thiazol-5-ylidene                                  
164  5-        4,5,5-trimethyl-2,5-dihydro-                               
                                 m.p. 145-147° C.                  
               thiazol-2-ylidene oil                                      
165  5-        cyclopentylidene  oil                                      
166  5-        1H-indan-1-ylidene                                         
167  5-        cyclohexylidene   oil                                      
168  5-        9H-fluoren-9-ylidene                                       
                                 m.p. 154° C.                      
__________________________________________________________________________
               R.sup.4   R.sup.5                                          
169  5-        p-tolyl   trifluoromethyl                                  
                                 oil                                      
170  5-        3-bromophenyl                                              
                         trifluoromethyl                                  
                                 oil                                      
171  5-        3-chlorophenyl                                             
                         trifluoromethyl                                  
                                 oil                                      
172  5-        2,4-dichlorophenyl                                         
                         2-fluorophenyl                                   
                                 oil                                      
173  5-        5-(1,3-benzodioxolanyl)                                    
                         cyclopropyl                                      
                                 oil                                      
174  5-        5-bromo-2-thienyl                                          
                         methyl  oil                                      
175  5-        5-methyl-2-furanyl                                         
                         methyl  oil                                      
176  5-        3-(α,α,α-                                
                         methyl  oil                                      
               trifluoro-m-                                               
               tolyloxy)-phenyl                                           
177  5-        2-chlorophenyl                                             
                         methyl  oil                                      
178  5-        4-bromophenyl                                              
                         methyl  m.p. 132-133° C.                  
179  5-        3-phenoxyphenyl                                            
                         hydrogen                                         
                                 oil                                      
180  5-        p-tolyl   hydrogen                                         
                                 m.p. 128-129° C.                  
181  5-        4-bromophenyl                                              
                         ethyl   oil                                      
182  5-        3,4-dimethoxyphenyl                                        
                         methyl  oil                                      
183  5-        4-ethylphenyl                                              
                         hydrogen                                         
                                 oil                                      
184  5-        2,4-dimethoxyphenyl                                        
                         methyl  oil                                      
__________________________________________________________________________
EXAMPLE 185
A solution of 10 g of dimethyl {3-(α-methoxycarbonyl-β-methoxyvinyl)-5-benzo[b]thienyl}methylphosphonate in 20 ml of tetrahydrofuran is added dropwise to a suspension of 1.3 g of sodium hydride in 30 ml of tetrahydrofuran. 3 ml of benzaldehyde are then added, and the reaction mixture is stirred for 2 hours at room temperature. It is subsequently concentrated, and water is added, and the mixture is extracted with ethyl acetate. The organic phase is dried over anhydrous sodium sulfate and concentrated under reduced pressure, and the residue is then purified by chromatography on silica gel using methylene chloride/n-hexane (1:1). Recrystallization from methylene chloride/ethyl acetate/n-hexane gives methyl α-(5-styryl-3-benzo[b]thienyl)-β-methoxyacrylate as colourless crystals, m.p. 180°-181 ° C.
EXAMPLES 186-188
Analogously to the process described in Example 185, dimethyl {3-(α-methoxycarbonyl-β-methylvinyl)-5-benzo[b]thienyl}methylphosphonate is reacted with the aldehyde in question, of the formula V, to prepare the compounds of the formula I listed in Table 4 below:
              TABLE 4                                                     
______________________________________                                    
 ##STR13##                                                                
       Position of                                                        
Example                                                                   
       R.sup.1 CHCH                                                       
                   R.sup.1     Physical data                              
______________________________________                                    
186    5-          α,α,α-tri-                           
                               m.p. 145-146° C.                    
                   fluoro-m-tolyl                                         
187    5-          3-thienyl   m.p. 214-215° C.                    
188    5-          2-pyridyl   m.p. 126-127° C.                    
______________________________________
EXAMPLE 189
A mixture of 0.9 g of methyl α-(5-formyl-3-benzo[b]thienyl)-β-methoxyacrylate, 0.3 ml of aniline and a catalytic amount of p-toluenesulfonic acid in 30 ml of ethanol is refluxed for 1 hour. The mixture is then concentrated under reduced pressure, saturated sodium hydrogencarbonate solution is added, and the mixture is extracted three times using ethyl acetate. The combined organic phases are dried over anhydrous sodium sulfate and then concentrated. This gives methyl α-(5-phenylimino-3-benzo[b]-thienyl)-β-methoxyacrylate as yellow crystals, m.p. 152° C.
EXAMPLES 190-205
Analogously to the process described in Example 189, methyl α-(5-formyl-3-benzo[b]thienyl)-β-methoxyacrylate is reacted with the amine or hydroxylamine in question, of the formula VII, or with hydrazine, of the formula VIII, to prepare the compounds of the formula I listed in Tables 5 and 6 below.
              TABLE 5                                                     
______________________________________                                    
 ##STR14##                                                                
       Position of                                                        
Example                                                                   
       R.sup.6 CHCH                                                       
                   R.sup.6      Physical data                             
______________________________________                                    
190    5-          methoxy      m.p. 148-149° C.                   
191    5-          ethoxy       m.p. 98-99° C.                     
192    5-          allyloxy     m.p. 83-84° C.                     
193    5-          benzyloxy    m.p. 142-143° C.                   
194    5-          4-chlorobenzyloxy                                      
                                m.p. 134-135° C.                   
195    5-          3,4-dichloro-                                          
                                m.p. 142-143° C.                   
                   benzyloxy                                              
______________________________________                                    

                                  TABLE 6                                 
__________________________________________________________________________
 ##STR15##                                                                
     Position of                                                          
Example                                                                   
     R.sup.7 R.sup.8 NNCH                                                 
               R.sup.7 R.sup.8 N                                          
                             Physical data                                
__________________________________________________________________________
196  5-        dimethylamino m.p. 172-173° C.                      
197  5-        phenylamino   m.p. 229-233° C.                      
                             (with decomposition)                         
198  5-        p-tolylsulfonylamino                                       
                             m.p. 162-167° C.                      
                             (with decomposition)                         
199  5-        6-chloro-2-pyridylamino                                    
                             m.p. 195-196° C.                      
200  5-        3-chloro-5-trifluoromethyl-                                
                             m.p. 217-218° C.                      
               2-pyridylamino                                             
201  5-        2-pyridylamino                                             
                             m.p. 221-222° C.                      
202  5-        7-chloro-4-quinolinylamino                                 
                             m.p. 159-161° C.                      
203  5-        4,6-dimethyl-2-pyrimidinyl-                                
                             m.p. 161° C.                          
               amino                                                      
204  5-        6-methyl-4-trifluoromethyl-                                
                             m.p. 186-188° C.                      
               2-pyridylamino                                             
205  5-        (methyl)6-methyl-4-trifluoro-                              
                             m.p. 225-226° C.                      
               methyl-2-pyridyl)amino                                     
__________________________________________________________________________
II. Preparation of the starting materials of the formula IV
EXAMPLE 206
A mixture of 20 g of methyl α-(5-bromomethyl-3-benzo[b]thienyl)-β-methoxyacrylate (see Example 11), 7.1 ml of the trimethyl ester of phosphorous acid and 3.5 ml of toluene is refluxed for 2 hours. The mixture is then concentrated under reduced pressure, and the oil which remains is purified by chromatography on silica gel, namely first using ethyl acetate and subsequently using ethyl acetate/methanol (9:1 ). This procedure gives dimethyl {3-(α-methoxycarbonyl)-β-methoxyvinyl)-5-benzo[b]thienyl}methylphosphonate as a yellow oil.
III. Preparation of the starting materials of the formula VI
EXAMPLE 207
A mixture of 2 g of methyl α-(5-bromomethyl-3-benzo[b]thienyl)-13-methoxyacrylate (see Example 11), 16 ml of dimethyl sulfoxide and 0.5 g of sodium hydrogencarbonate is heated at 85° C. for 2.5 hours. Water is subsequently added, and the mixture is extracted using ethyl acetate. The organic phase is dried over anhydrous sodium sulfate and concentrated under reduced pressure, and the residue is then purified by chromatography on silica gel using diethyl ether/n-hexane (2:1). Recrystallization from methylene chloride/n-hexane gives methyl α-(5-formyl-3-benzo[b]thienyl)-β-methoxyacrylate as colourless crystals, m.p. 134°-135° C.
IV. Formulation examples
EXAMPLE 208
An emulsifiable concentrate consists of the following:
______________________________________                                    
                       g/liter                                            
______________________________________                                    
Active substance (compound according to                                   
                         100                                              
the invention)                                                            
Nonylphenol (10)ethoxylate (non-ionic                                     
                         50                                               
emulsifier)                                                               
Calcium dodecylbenzenesulfonate (anionic                                  
                         25                                               
emulsifier)                                                               
N-methyl-2-pyrrolidone (solubilizer)                                      
                         200                                              
Alkylbenzene mixture (solvent)                                            
                         to 1     l                                       
______________________________________
The active substance and the emulsifiers are dissolved in the solvent and in the solubilizer. A ready-for-use spray liquor of any desired concentration can be prepared by emulsifying this concentrate in water.
EXAMPLE 209
A wettable powder consists of the following:
______________________________________                                    
                   Percent per weight                                     
______________________________________                                    
Active substance (compound according                                      
                     25.0                                                 
to the invention                                                          
Silica (hydrated; carrier)                                                
                     20.0                                                 
Sodium lauryl sulfate (wetting agent)                                     
                     2.0                                                  
Sodium lignosulfonate (dispersant)                                        
                     4.0                                                  
Kaolin (carrier)     49.0                                                 
______________________________________
The components are mixed with each other, and the mixture is ground finely in a suitable mill. Dispersion of the mixture in water gives a suspension which is suitable as a ready-for-use spray liquor.

Claims (18)

What is claimed is:
1. A compound of the formula ##STR16## in which R is halogen, C1-4 haloalkyl, C1-4 alkoxy-C1-4 alkyl, phenyl-C1-4 alkoxy-C1-4 alkyl, phenoxy-C1-4 alkyl, phenylthio-C1-4 alkyl, C2-5 alkanoyloxy-C1-4 alkyl, optionally C1-4 alkyl-substituted C3-6 cycloalkyl-carbonyloxy-C1-4 alkyl, benzoyl-C1-4 -alkyl, phenyl-C2-5 alkanoyloxy-C1-4 alkyl, C1-4 alkoxy, phenoxy or one of the groups ( a ) to ( e )
R.sup.1 CH═CH                                          (a)
R.sup.2 R.sup.3 NCH.sub.2                                  (b)
R.sup.4 R.sup.5 C═NOCH.sub.2                           (c)
R.sup.6 N═CH                                           (d)
R.sup.7 R.sup.8 N--N═CH                                (e),
R1 is phenyl,
R2 and R3 independently of one another are hydrogen,
C1-4 alkyl, phenyl-C1-4 alkyl or phenyl,
or R2 and R3 together with the nitrogen atom to which they are bonded form a 5- or 6-membered ring which may contain an oxygen or sulfur atom,
R4 and R5 independently of one another are hydrogen,
C1-4 alkyl, C1-4 haloalkyl, C1-4 alkoxy-C1-4 alkyl, C1-4 alkylthio-C1-4 alkyl, phenyl-C1-4 alkyl, C3-6 cycloalkyl, phenyl, C1-4 alkoxy or benzoyl,
or
R4 and R5 together with the carbon atom to which they are bonded form (1) a 5- or 6-membered heterocyclic ring having up to two hereto atoms selected from N and S or (2) a 5- or 6- membered carbocyclic ring to which one or two benzene rings may be fused,
R6 is phenyl, C1-4 alkoxy, phenyl-C1-4 alkoxy or C3 or 4 alkenyloxy,
and
R7 and R8 independently of one another are hydrogen,
C1-4 alkyl, phenyl, or phenylsulfonyl;
the foregoing phenyl substituents being unsubstituted or substituted by a substituent selected from the group consisting of halogen, C1-4 alkyl, C1-4 haloalkyl, C1-4 alkylthio-C1-4 alkyl, C1-4 alkoxy, C1-4 haloalkoxy, phenyl-C1-4 alkoxy, C1-4 alkenyloxy, phenoxy, C1-4 alkylthio, C1-4 cycloalkyl-C1-4 alkylthio, nitro and tri(C1-4 alkyl)silyl.
2. A compound as claimed in claim 1, in which the substituent R is in the 5-position of the benzo[b]thiophene ring.
3. A compound as claimed in claim 22 in which halogen, C1-4 haloalkyl, C1-4 alkoxy-C1-4 alkyl, phenoxy-C1-4 alkyl, phenylthio-C1-4 alkyl, C1-4 alkoxy, phenoxy or one of the groups (a) to (d), R1, R2 and R3 are as defined in claim 2, and R4 and R5 independently of one another are hydrogen, C1-4 alkyl, C1-4 haloalkyl, C1-4 alkoxy-C1-4 alkyl, C3-6 cycloalkyl or phenyl and R6 is phenyl.
4. A compound as claimed in claim 3, selected from amongst
Methyl α-(5-(α-methyl-m-trifluoromethylbenzylideneaminooxymethyl)-3-benzo[b]thienyl}-β-methoxyacrylate,
methyl α-{5-(α-[n-propyl]-benzylideneaminooxy-methyl)-3-benzo[b ]thienyl}-g-methoxyacrylate,
methyl α-{5-(α-cyclopropyl-4-chlorobenzylideneaminooxymethyl)-3-benzo[b ]thienyl}-β-methoxyacrylate,
methyl α-{5-methoxy-3-benzo[b]thienyl}-β-methoxyacrylate,
methyl α-{5-ethoxy-3-benzo[b]thienyl}-13-methoxyacrylate,
methyl α-{5-[(α-phenylethyl)methylaminomethyl]-3-benzo[b]thienyl}-.beta.-methoxyacrylate,
methyl α-{5-(dicyclopropylmethylideneaminooxymethyl)-3-benzo[b ]thienyl}-β-methoxyacrylate,
methyl α-{5-(α-cyclopropyl-m-trifluoromethylbenzylideneaminooxymethyl)-3-benzo[b]thienyl}-β-methoxyacrylate.
5. A compound as claimed in claim 1, selected from amongst:
methyl α-{5-(α-cyclopropylbenzylideneaminooxymethyl)-3-benzo[b ]thienyl}-β-methoxyacrylate,
methyl α-{5-[g-methyl-α-(2-pyridyl)-propylideneaminooxymethyl]-3-benzo[b ]thienyl}-β-methoxyacrylate and
methyl α-{5-(2-isopropyl-4-methyl-2,5-dihydrothiazol-5-ylideneamino oxymethyl)-3-benzo[b]thienyl}-β-methoxyacrylate.
6. A compound as claimed in claim 3, in which the substituent R is in the 5-position of the benzo[b]thiophene ring.
7. The compound methyl α-{5-(α-methyl-m-[α,α,α-trifluoro-m-tolyloxy]-benzylideneaminooxymethyl)-3-benzo[b]thienyl}-β-methoxyacrylate.
8. A fungicidal composition which contains an effective amount of a compound as defined in claim 1 and formulation auxiliaries.
9. A fungicidal composition as claimed in 8, which contains an effective amount of a compound selected from the group consisting of:
methyl α-{5-(α-methyl-m-trifluoromethylbenzylideneaminooxymethyl)-3-benzo[b]thienyl}-β-methoxyacrylate,
methyl α-{5-(α-[n-propyl]-benzylideneaminooxy-methyl]-3-benzo[b]thienyl}-β-methoxyacrylate,
methyl α-{5-(α-cyclopropyl-4-chlorobenzylideneaminooxymethyl)-3-benzo[b]thienyl}-β-methoxyacrylate,
methyl α-{5-methoxy-3-benzo[b]thienyl}-β-methoxyacrylate,
methyl α-{5-ethoxy-3-benzo[b]thienyl}-β-methoxyacrylate,
methyl α-{5-[(α-phenylethyl)methylaminomethyl]-3-benzo[b]thienyl}-.beta.-methoxyacrylate,
methyl α-{5-(dicyclopropylmethylideneaminooxymethyl)-3-benzo[b]thienyl}-.beta.-methoxyacrylate,
methyl α-{5-(α-cyclopropyl-m-trifluoromethylbenzylideneaminooxymethyl)-3-benzo[b]thienyl}-β-methoxyacrylate,
and also formulation auxiliaries.
10. A fungicidal composition as claimed in claim 8, which contains an effective amount of a compound selected from the group consisting of:
methyl α-{5-(α-cyclopropylbenzylideneaminooxymethyl)-3-benzo[b]thienyl}-β-methoxyacrylate,
methyl α-{5-(2-isopropyl-4-methyl-2,5-dihydrothiazol-5-ylidene aminooxymethyl)-3-benzo[b]thienyl}-β-methoxyacrylate,
and also formulation auxiliaries.
11. A method of controlling fungi in agriculture and in horticulture, which comprises treating the goods to be protected with an effective amount of a compound as claimed in claim 1.
12. A method of controlling fungi in agriculture and in horticulture, which comprises treating the goods to be protected with an effective amount of a compound as claimed in claim 1.
13. A method according to claim 11 wherein the compound is a compound wherein the substituent R is in the 5-position of the benzo[b]thiophene ring.
14. A method according to claim 11 wherein the compound is a compound selected from the group consisting of methyl α-{5-(α-cyclopropylbenzylideneaminooxymethyl)-3-benzo[b]thienyl}-β-methoxyacrylate, and methyl α-{5-(2-isopropyl-4-methyl-2,5-dihydrothiazol-5-ylideneamino oxymethyl)-3-benzo[b]thienyl}-β-methoxyacrylate.
15. A method for controlling fungi in agriculture or horticulture which comprises treating goods to be protected with a composition as defined in claim 10.
16. A method for controlling fungi in agriculture or horticulture which comprises treating goods to be protected with a composition as defined in claim 10.
17. A method for controlling fungi in agriculture or horticulture which comprises treating goods to be protected with an effective amount of a compound as defined in claim 4.
18. A method for controlling fungi in agriculture or horticulture which comprises treating goods to be protected with an effective amount of a composition as defined in claim 9.
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US5534487A (en) * 1995-05-16 1996-07-09 Rohm And Haas Company Stabilization of 3-isothiazolone solutions
US5606075A (en) * 1995-06-07 1997-02-25 Eli Lilly And Company Process for the synthesis of benzo[b]thiophenes
US5608080A (en) * 1993-09-27 1997-03-04 Ihara Chemical Industry Co., Ltd. Process for production of 2-substituted benzo[b]thiophene
US5728696A (en) * 1992-04-22 1998-03-17 Hoechst Aktiengesellschaft Acaricidal, insecticidal and nematicidal substituted (hetero)arylalkyl ketone oxime O-ethers, processes for their preparation, agents containing them, and their use as pesticides
US6084120A (en) * 1997-07-09 2000-07-04 Hoffmann-La Roche Inc. β-Alkoxyacrylates against malaria
US20050014943A1 (en) * 2000-06-23 2005-01-20 Glasky Alvin J. Methods of synthesis for 9-substituted hypoxanthine derivatives
USD705442S1 (en) 2013-04-15 2014-05-20 Hu-Friedy Mfg. Co., Llc Latch for a sterilization cassette
WO2015168010A1 (en) 2014-04-29 2015-11-05 E. I. Du Pont De Nemours And Company Pyridazinone herbicides
USD764067S1 (en) 2012-06-16 2016-08-16 Hu-Friedy Mfg. Co., Llc Sterilization cassette
WO2017074992A1 (en) 2015-10-28 2017-05-04 E. I. Du Pont De Nemours And Company Novel pyrdazinone herbicides
WO2018183432A1 (en) 2017-03-28 2018-10-04 Fmc Corporation Novel pyridazinone herbicides
WO2021219778A1 (en) * 2020-04-30 2021-11-04 Syngenta Crop Protection Ag Microbiocidal compounds

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US5258360A (en) * 1986-04-17 1993-11-02 Imperial Chemical Industries Plc Alphamethoxy acrylic acid derivatives as fungicides
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IL115894A0 (en) * 1994-12-08 1996-01-31 Du Pont Organosilanes and organogermanes and their use
JP2021028298A (en) * 2017-11-30 2021-02-25 日本曹達株式会社 1,3,5,6-tetrasubstituted thieno[2,3-d]pyrimidine-2,4(1h,3h)dione compound, and agricultural and horticultural fungicide
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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5728696A (en) * 1992-04-22 1998-03-17 Hoechst Aktiengesellschaft Acaricidal, insecticidal and nematicidal substituted (hetero)arylalkyl ketone oxime O-ethers, processes for their preparation, agents containing them, and their use as pesticides
US5608080A (en) * 1993-09-27 1997-03-04 Ihara Chemical Industry Co., Ltd. Process for production of 2-substituted benzo[b]thiophene
US5534487A (en) * 1995-05-16 1996-07-09 Rohm And Haas Company Stabilization of 3-isothiazolone solutions
US5606075A (en) * 1995-06-07 1997-02-25 Eli Lilly And Company Process for the synthesis of benzo[b]thiophenes
US6084120A (en) * 1997-07-09 2000-07-04 Hoffmann-La Roche Inc. β-Alkoxyacrylates against malaria
US20050014943A1 (en) * 2000-06-23 2005-01-20 Glasky Alvin J. Methods of synthesis for 9-substituted hypoxanthine derivatives
USD764067S1 (en) 2012-06-16 2016-08-16 Hu-Friedy Mfg. Co., Llc Sterilization cassette
USD705442S1 (en) 2013-04-15 2014-05-20 Hu-Friedy Mfg. Co., Llc Latch for a sterilization cassette
USD764068S1 (en) 2013-04-15 2016-08-16 Hu-Friedy Mfg. Co., Llc Sterilization cassette
USD721441S1 (en) 2013-04-15 2015-01-20 Hu-Friedy Mfg. Co., Llc Sterilization cassette
WO2015168010A1 (en) 2014-04-29 2015-11-05 E. I. Du Pont De Nemours And Company Pyridazinone herbicides
EP3865480A1 (en) 2014-04-29 2021-08-18 FMC Corporation Hydrazine derivatives
WO2017074992A1 (en) 2015-10-28 2017-05-04 E. I. Du Pont De Nemours And Company Novel pyrdazinone herbicides
WO2018183432A1 (en) 2017-03-28 2018-10-04 Fmc Corporation Novel pyridazinone herbicides
WO2021219778A1 (en) * 2020-04-30 2021-11-04 Syngenta Crop Protection Ag Microbiocidal compounds

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